Process for treating mineral oils



Dec. 3l, 1929. A. H. ACKERMAN Pnocss FOR TREATING MINERAL ons Original Filed Dec. 14, 1925 kwttws dwg iQ Maw il@ Patented Dec. 31, 1929 UNITED STATES PATENT oFl-*lclaV ALBERT H; ACKERMAN, OF CHICAGO, ILLINOIS, `ASSIGNOIR TO CATALYTIC CHEMICAL COMPANY, A CORPORATION OF COLORADO PROCESS FOR TREATING MINERAL OILS Application led December 14, 1925, Serial No. 75,472. Renewed April 15, 1929.

My invention relates to processes of treating mineral oils and products containing carbon, particularly when in the form of hydrocarbons, and to the materials and methods of compounding the same for'use in carrying out the processes.

The processes are particularly designed for the treatment of petroleum products in which is foundcarbon clustered or massed 'together so that the quality of the products may be affected or they may be of inferior grade, or which products may not be treated as eiiciently as possible by the various refining processes employed and a more or less complete recovery of desired products made. My processes and materials are designed to be used with or without other treatments or processes, depending upon the materials treated, with'out aifecting those processes eX- cept as it may improve the same, resulting in better products, increased yield, or in economy in the carrying out of present methods.

My invention has among its objects the production of suitable materials for carrying out my improved processes of treating hydrocarbons, and improved processes, and in such a manner that waste products may be recovlxred and be marketable. For example, the

3o residuum from cracking plants, heretoforean expensive waste product, may be transformed into a valuablemarketable product. It also has among its objects an improved process of treating what is known as lubricating oil stock from which lubricating oil is manufactured, or the treatment of cracking stock. It has also as anv object an improved process for cleaning and keeping clean and unobstructed pipe lines in which waxes and the like accumulate, thereby tending to reduce the flow through the pipe line, as well as increase the cost of pumping. My invention has among its further objects the increasing of the eiiiciency for fuel oil by processing the same with treated petroleum coke, as will be more fully set forth hereinafter. Further objects and advantages and applications of my present invention will more particularly appear from the specific explanation of ma.-

60 terials used and treatments followed, as well as products treated, as will be hereinafter set forth and more particularly pointed out in the claims.

For a better understanding of the nature, scope and characteristic features of my present invention, reference may be had to the following description and the accompanying drawing which is a simple diagrammatic represent-ation employed'. only for the purpose of illustration of a process for treating mineral oils or petroleum in order to procure therefrom the various products and by-products which are utilized inindustry. It is to be understood that the diagram and the description pertaining thereto is illustrative only and solely for the purpose of explaining my invention and its application at various points in the processing of petroleum, for the procurement of the various petroleum products that are of commercial importance.

My invention is not to be limited to any specific method of treating petroleum in order to secure the commercial products therefrom,

vbut is capable of broadapplication to different petroleum products in order to improve their quality and enhance their propertiesirrespective of the method employed in securing the petroleum products that I treat in accordance with my invention.

My invention can best be understood by first outlining briey a method of processing petroleum in order to secure therefrom the various commercial products which I treat in order to purify them, recover them, or make them more acceptable, more efiicient, ormore marketable products.

To this end reference may be had to the accompanying drawing showing diagrammatically one process of treating crude petroleum to recover the by-products therefrom, the arrows in the drawing indicating various points where my present invention is applicable in treating the materials being processed, but it is to be understood that my invention is not to be limited solely to these points so indicated since my invention is aplicable to a variety of points in the processing of crude petroleum. Y

To illustrate, the crude petroleum is drawn from the well and delivered,l1.$l1a11y through pipe lines, to a storage tank or tanks known i as tank farms, from which the petroleum as required is fed to a still or other apparatus.` From the still certain products are secured, among which may be enumerated the light hydrocarbons such as the naphthas, gasoline, burning oils, etc., whichneed not be enumerated in full. There is also obtained the distillate which forms4 .cranking stock whichv passes to the crackers and lubricating stock which is employed in the manufacture of lubricatin oil. The products 4obtained from the distillate by the cracking processes are for example, fixed gas, gasoline, kerosene, and the aromatic hydrocarbons, gasoline being the principal product and most desired. After the light hydrocarbons have been secured from the crackers, there remains a material known as the residuum, which has heretofore generally been a waste product. At the present time it is customary to, provide dumps or earth reservoirs and carry out this waste product or residuum from the crackers and discharge it into these dumps, and it has been usually considered as a product without Value, and so far as I know, prior to my method of treating, the same has been a total waste product in many instances. The refiners in many instances not only cross this off the books as a loss or waste, but in addition it is an expensive waste product as the same must be handled and transported far enough away from the refinery -so as not to interfere with future operations or increase fire hazards, and vobviously comparatively large areas are required for its storage, as well as the expense of constructing reservoirs for containing thesame.-

This material may vary in its consistency 0r viscosity, and generally it is a semi-solid material or heavyemulsion. I have' found the same in many instances the consistency of a very irm jelly which may be often handled by shoveling as it is too thick to Vrun or flow, and it consists of hydrocarbon clusters, some free carbon, and a percentageof other byproducts, depending upon the baseof oil or stock which was subjected to the cracking process. Immediately taken from the crackers, it, of course, does not contain water or moisture to any appreciable extent, although, of course, if it is old residuum in the dumps it may have accumulated some water from the weather.

Vtransform the oil into la free flowing fluid onto make it amore mobile liquid at ordinary temperatures so that it can be easily pumped, I am not aware that it has ever been 'proposed to treat or process residuum secured from oilvcrackers, which is known in the art as a Waste product, 1n order v,to make it utilizable as a commercial product or to' reclaim it as a viscous fuel oil possessing high B.t;u. value.-

The part of the distillate from the stills known as lubricating stock, generally called stock, is treated in various ways for the p'urpose of securing lubricating oils as a petroleum product. Usually this is discharged into an agitator` and treated with sulphuric acid during heating and agitation. From the agitator lubricating oil requiring further treatments and a residuum known -as acid sludge are secured, which isat the present time a waste product. Theacidulating and agitating process may be repeated at different times and need not be described in detail. In some instances it has'been found that 'the lubricating stock is not adapted for the manufacture of lubricating oil, or that to treat the same so much sulphuric acid is reunsatisfactory, as for example, Where the base product was from the Lost Soldier field, and in all instances it is possible to secure the lubricating oil with the use of less acid. i

In connection with pipe lines, the crude petroleum may be pumped from the Wells to the tank farms or tank farms to the stills. Where the distance from the well to the tank farm is very great, it is customary to have pumping and heating stations at intermediate points asv the oil has a tendency to chill and its viscosity increase, causing a deposit of parafine and other waxes and various products in the pipe lines so that, for example, a six inch pipe line might be so obstructed that it was only equivalent to a two inch pipe. In this instance it is necessary to clean the pipe lines, and in so far as I know, this has never been proposed in the manner in which I have proposed todo it. By the employment of my process and materials used in carrying Aout the process, not only is the and naphthalene.

pipe line cleaned, but by the continued used of the materials the pipe line is maintained clean or unobstructed so that there is an immediate saving in pumping and heating ex.

pense, and initial equipment is reduced in cost as smaller size pipe lines may be employed. y

My treatments or processes -may be employed at other steps or points in the flow of the materials between the wells and the market, and has been, for example, found desirable and of value in treating cracking stock either as it comes from'the crude stills andV prior to entering the cracker, or during the cracking process, as for example, after it has been subjected to heat in the furnace or heating coils and prior to its admission to the re action chamber or while in the same or in similar or other apparatus employed in cracking processes.

`My treatments or processes may likewise be employed for the treatment of petroleum coke which is generally considered as a waste product but by means of which I am able to enrich fuel oil and increase the B. t. u. value to a very considerable extent.

By the employment of my processes and materials, all hydrocarbon clusters, regard# less of the nature of the products in which they may be found, whether in the hydrocarbons, that is, the lighter groups, or in the paraliine, residuum or the like, are broken down and in such a manner that there is no re-formation of the clusters, except as there may be re-formingr of clusters in the different products produced. In other words, the herein described difficulties have been overcome.

Referring now to the treatment of cracking still residuum which, as before stated, comprises hydrocarbon clusters of various kinds, some free carbon and percentages of other hydrocarbon products, depending upon the particular field from which the oil is taken, as Well as the/ various refinery processes through which the residuum hasv previously passed, I subject this residuum at the time of addition of the chemicals herein set forth to agitation, either compressed air jets or any equivalent agitation, so as to cause a thorough chemical treatment of the entire mass of residuum.

The materials which I employin the treatment of the residuum are anthracene, oil of mirbane, sulphuric acid, sodium hydroxide In making up my composition of materials, while the same may be combined in various ways, I have secured satisfactory results and prefer to combine it in substantially the manner and as follows:

l() lbs. anthracene, 4 lbs. oil mirbane, 2 lbs. sulphuric acid, l lb. sodium hydroxide. These ingredients are mixed together until a heavy paste is formed by iirst mixing the anthracene with the sulphuric acid, and then addin the oil of mirbane and then the sodium ydroxide, the same being permitted to stand in the open air for a period, generally for one hour. This mixture is then added to substantially 200 lbs. of flake naphthalene and the whole ground in a ball mill for the desired time. two hours being generally the period for which I grind it. It appears that the treatment of the naphthalene in this man ner prevents the naphthalene and also any of the other products in themselves from forming waxes or other products. In treating the `residuum or the like,'I"'usuall treat the same 1n he proportion of 1 1b. o my mixture to approximately 8 bbls. of the residuum, agitating the're'siduum as previously mentioned. In some instances in the treatment of fuel ,Y oil residuum4 or other` similar products the :proportlons may be varied, and I have found thatin some cases only l lb. of the materials need be used to 20 bbls. of the product to be treated.

. The purpose of treating the anthracene with the sulfuric acid, as stated in the preceding paragraph, is to render the same more readily soluble in the oil products to be treated. The sulfuric acid appears to remove or destroy certain impuritiesin the anthracene. If, however, 85% pure anthracene is used in the composition, this sulfuric acid treatment becomes unnecessary. For reasons of expense, however, the common 40% green anthracene is preferred, and this requires the sulfuric acid treatment. The sodium hydroxide added later is forthe purpose of removing 0r neutralizing any excess of sulfuric acid that might remain after the action of the latter on the anthracene, as the sulfuric acid, as such, is not needed in the final composition.

In its action the naphthalene acts as a cutter in separating the hydrocarbon clusters, the same to some extent acting like a miniature explosion, the action being observable when seenV under a powerful microscope. The anthacene when thoroughly co-mixed with the naphthalene, as is the case here, appears to slow up the action of the naphthalene and to a certain extent retard it so that it has sufficient time to perform its work or function and thoroughly disintegrate the carbon clusters. The oil of mirbane decreases the fusing point of both the anwell. When I mention oil of mirbane herein, it is to be understood that naphtha may be substituted for it and that, for` the purposes herein specilied, is an equivalent of oil or mirbane. 4

It may be mentioned that in some instances where the material to be treated is a light oil residuum or the like, I have found that treatment with a composition of materials consisting 0f naphthalene, anthracene and sodium hydroxide greatly improves the residuum and enhances its value. However, it isrgenerally preferred to treatirthe oil with the regular composition mixture previously set forth rather thanwith a modified one.

In the treatment of pipe lines to clean them or keep them clean, I apply my ma.- terials or mixtures` to the crude stock as it comes from the well, although the same may be applied in the well or at various points in its flow, as will be hereinafter referred to. For 'this treatment, I prefer to use a combination of materials that will break up the carbon clusters, waxes, binders, fats, etc., so that the petroleum remains more fluid and does not have a tendency to clog the lines. I.

have found a very satisfactory mixture to lconsist of flake naphthalene or a. substitute,

anthracene, a. combination nof alkali which I prefer to make up with caustic soda, sodium phosphate, and ammonium carbonate, together with granulated sugar, a phosphate rock or powder or the equivalent, and a limited amount of sulfuric acid. For the phosphate rock, I have secured very satisfactory results using a Florida phosphate rock or powder analyzing approximately as follows: carbon dioxide, silica, phosphorus, pentoxide, lime, alumina (including a tra-ce of ferrie oxide as iron), magnesia, and luorine. I

` prefer the natural phosphate rock rather than a made-up combination of ingredients, and I find that slight variations in the analysis of the rocks do not affect the treatments to any extent. As an illustration, I have secured satisfactory results by the-use of 133 lbs. naphthalene, 21 lbs. anthracene, 58 lbs. caustic soda, 10 lbs. sodium phosphate,

' 10 lbs. ammonium carbonate, 2O lbs. granuvthen add the granulated sugar and grind that for several minutes. See my copending application, Serial No. 168,819, filed as a division of my copending application, Serial No. 76,901, filed December 21st, 1925. The material is'then dum ed `"and 'packed in airtight metal drums or use.

When used, it is applied to the crudeoil inr a proportion of about 1 lb. to every 30 bbls. oil, the proportions depending on the particular oil to be treated, which is readily determined by testing. e Where tank stock A.or

residuum is treated, I treat in the proportion generl ly of 1 1b. to 15v bbls. of petroleum,

from the crackers, it is impossible to state exactly the chemical action due to the adding of the caustic soda, sodium phosphate or ammonium carbonate, but these apparently, when added to the petroleum from the well, produce an artificial heat by chemical action and cooperate with the other chemicals in separating the hydrocarbon clusters, the same by chemical action increasing the temperature sufficiently to cause a permanent change of the cold test range of the oils or large bodies of hydrocarbons. These also work with the granulated sugar, it having been found after much experimenting that there was a. chemical action creating more iiuid substance. Of course, I know that in adding the sugar, I have added a percentage of moisture in itself, and taking the alkalis referred to with the sugar, there is a catalytic action on the hydrocarbon clusters, breaking them and making a more permanent fluid. Presumably the alkali 'addition breaks up ,the binders or cuts the binder the same as they would cut fats. By the attack that the combination makes on the binder that holds the clusters together, together with the naphthalene and anthracene which has a milder effect on separating the clusters, the binder is destroyed so that the same is not formed again Vin the pipe lines or containers 'so far as the clusters in the parafiine wax, asphalt or tar. The parafline wax, tar or asphalt alone may be cut by the caustic soda, ammonium carbonate and granulated sugar mixture, Without the presence of carbon in the wax as I have successfully demonstrated this, to-wit, by adding the combination to crude oil where it has the presence of a large quantity of gasoline and dierent groups of oils of low specific gravities. I found that there was a cutting action on the paraiine or wax combination so that they would not adhere at temperatures as low as 45 F., thereby indicating that the cold test is lowered.

The lubricating oil stock previously referred to is ordinarily a residuum which consists of heavy thick mass of h' drocarbons and waxes, dependin on the ase of the oil or the field from w ich it is taken, after the light ends, gases, oil and kerosene, etc., are distilled off at temperatures around 500 to 550 F. In order to make lubricating oil from this grade of material it is necessary to remove substantially all of the heavy ends of carbonand also the waxes, to extract the pure oil. When this is treated in the agitator with heat, agitation and by the addition of sulphuric acid, a violent chemical reaction takes place and the heavy carbons, ory heavy residue of a carbon nature, is dropped to the bottom of the agitator. The thinner mass of HuidI is on the top. The amount of acid required depends on the grade of lubricating stock treated, and this amount varies with whether it is the first or second, etc., treatment, or the particular base which may be used. It is considered dangerous to use an excess acid as it will stay in the thinner oil as the heavy carbons are dropped out, injuring the value of the oil for lubricating purposes.

My treatment is applied to the lubricating stock preferably at the time of discharge into the agitator or prior thereto, the same reacting `as hereinafter set forth. I have found as a result of tests that a less amount of acid is required when my treatment is carried out, and I have found in someffinstances it is possible to make lubricating oil from some lubricating stocks where before it was impossible owing to the amount of acid required to get the break. rIoo much acid will cause so rapid a break as to clog the agitator in some instances. This was found true in the case of oil from Lost Soldier field previously referred to.

In treating or carrying out my process, however, I find that certain additional chemicals are desirable in order to produce a better product, although the product is improved by using either of the combinations previously mentioned. I have further found that the color may be improved by the addition of de-colorizers. y

In the process of treating lubricating stock, I prefer to use the flake naphthalene, anthracene, caustic soda, sodium` phosphate, ammonium carbonate, granulated sugar, phosphate rock, and in addition aresenious acid (white powder), arsenic sulfide (yellow powder), and golden antimony sulfide, these last three being particularly designed to improve the color. Imrnaking up a batch, the ingredients may be combined, for example, in approximately the following proportions, it being understood that the quantity required depends upon the amount of lubricating stock to be treated and that the proportions set forth are substantially approximate and may be varied within limits, depending upon the particular base from which the lubricating stock was 'derived.`I have secured satisfactory results when employing thev materials in the proportion of 120 lbs..flake naphthalene, 100 lbs. phosphate rock, 35 lbs. caustic soda, 18 lbs. anthracene, 6% lbs. ammonium carbonate, 61/2 lbs. sodium phosphate, 15 lbs. granulated sugar, 1 lb. arsenious acid, 1 lb. arsenic sulfide, and 1 lb. golden antimony sulfide. This mixture is ground for an hour or more, and then there is added to the same 1 lb. more or less of oil of mirbane liquid.

In using the materials, I use ordinarily one-sixth pound per barrel of lubricating stock, but this may vary from a sixth or more down to a twelfth of a pound per barrel of lubricating stock, depending upon the particular kind of stock treated. After treatment thereafter inthe usual manner, it is found that the heat and sulphuric acid treatment in the agitator is greatly improved. The chemicals cause a breaking up ofthe carbon clusters, and there is a better break between the sulphuric acid and the oil. There is a chemical reaction raising the temperature and breaking up the smaller hydrocarbon clusters that the acid would ordinarily not attack suiiiciently to cause them to separate by gravity from the oil. The phosphate rock seems to greatly improve the action, causing the acid to break quicker and cut sharper with smaller quantities of acid and to bring a better color to the oil. Ordinarily the chemicals are put in about three to five minutes before the sulphuric acid is added, and it was found that the temperature immediately went up several degrees, and after the sulphuric acid was added there was a violent boiling created and the heavy sludge or heavy carbons formed immediately and dropped to the bottom of the agitator, leaving the light oil and waxes at the top. As a result of this treatment, a very high grade of lubricating oil can be made from the Lost Soldier crude oil stock where before it was not possible to procure the same, owing to the amount of acid required. The sulphuric acid subsequent to the addition of my materials appears to make the attack or create the chemical action in a most satisfactory manner, presumabl due to the fact that I have separated the hy rocarbon clusters before adding the acid, creating a more fluid substance and making it easier for the acid to attack the heavy carbons. In practice I have found that the result is apparent for when excess quantities of my materials are used, the sulphuric acid will work so fast the sludge will drop so quickly that it will clog the agitator and it is difficult to handle the same and transport it away from the agitator.

In employing my invention in the treatment of cracking-still stock, I prefer generally to use the same materials as used forthe treatment of the stock in the pipe line previously referred to, except that the arsenious acid, the arsenic sulde and the timony sulide arsenic may be omitted, and as a matter of fact in some instances the phosphate rock or powder may also be omitted. Variations in the roportions of the ingredients may be modi ed to some extent, de ending upon the nature of the materials tolbe treated. The crackin -still stock may be treated in the pipe lines efore discharge into the cracking-still or at some step in the cracking'process. I have secured improved and satisfactory results, for illustration, in treating the oil in the expansion chamber or vaporizer or just prior to its discharge thereinto. As to the amount of my compound used in the above treatment, this may vary considerably, depending upon the particular materials to be treated or the previous treatments which it may have received prior to passing tothe cracker. I may mention, however, that I have secured ver satisfactory results in employing one poun of the composition of materials to each ten barrels of petroleum product so treated.

While I have secured satisfactory results from the use of the same materialsemployed in treating the cracking-still residuum as previously described, I generally prefer the composition with the combination alkali and sodium hydroxide in this treatment more or less as used for cleaning pipe lines. It may be mentioned that this treatmentfdn so far as I am able to determine from tests that have been made, increases the efficiency of the cracking process, and the residuum is improved, the same being more mobile and the clusters therein more thoroughly broken up so that in some instances the residuum may -be used without further treatment or by treatment with a greatly reduced quantity of my materials.

I have only mentioned a few of the possibilities of-my treatments of breaking up the hydrocarbon clusters. The treatments, probably in some cases with necessary additions or modifications, may broadly be utilized for treating the hydrocarbons and breaking up hydrocarbon clusters at various stages in the refinery or other operations. Ihave found that by'grin'ding' up petroleum coke, which is a hard coke substance, and adding, for example, my first materials mentioned as available on cracking-still residuum, during the operation of grinding, and then taking the entire mixture of chemicals with the dry pulverized petroleum coke and putting it back in the fuel oil, the fuel oil will dissolve a considerable percentage of the coke and increase the eiciency of the fuel oil from thirty to thirty-ve percent in energy heat or B. t. u. Iam not aware that such treatment of petroleum coke has ever been considered before. I therefore wisho be understood as including by the term cracking-still residuum any product which golden an-- amaeae p storage tanks, none of the waxes or the like' have been subjected to heat treatment other than the possible heat treatment used in sending it through the pipe lines at temperatures comparatively low as compared with the temperatures of thestills or the cracking-stills. The composition of material for treating residuum then does not need to take into consideration to any material extentvthe treatment of waxes or the like which have been broken down in the previous heat treatments. In lubricating oil or cracking stock, only those waxes that have survived the still need be treated with additional chemicals that are suitable to break them down in so far as possible. However, in the pipe lines, or crude oil from the well, all of the various waxes and fats, tars, asphalte, etc., as well as impurities, are in the crude oil. The composition of materials -for treating the crude oil must therefore perform an additional function or functions in more or less breaking down these waxes, fats or the like, so that the clusters therein may be treated. The breaking down of the clusters in the pipe lines may not be complete, depending on the nature of the crude oil, its source, etc. Also in the various processes following, or in the various refinery treatments, the carbons may re-cluster so that breaking down of 'clusters in the crude oil may not be permanent or suiiicient for all of the later products.

As before mentioned, the employment. of my compounds and processes at any step improves the eiciency of succeed-ing treatments or processes and apparatus so that even though I prefer to treat the petroleum in succeedin refinery steps, the refining processes are improved by preceding treatments so that there is a general improvement at all points between the crude in the well and the products to be marketed.

Having thus described my invention, it is obvious that in view of the many varied conditions under which petroleums and their products are treated and the various piocesses and the varied apparatus employed in refining and treating them, as well as the varied characteristics ofthe petroleums and their products, that considerable variation may be made from the above disclosure without departin from the spirit of my invention as set orth in the appended claims, whichshould be construed accordingly..

What I claim as new and desire to secure by Letters Patent is:

1. A method ot' treating a petroleum product consisting in breaking up the carbon clusters therein by the addition of a composition resulting from admixture of suitable substances comprising naphthalene and sodium hydroxide, and agitating the said petroleum products by air jets.

2. The process of treating petroleum products which comprises subjecting the same to the action of a composition resulting from the admixture of materials comprising i' anthracene, sulfuric acid, oil of mirbane, sodium hydroxide and naphthalene.

3. The process of treating petroleum products which comprises subjecting the same to the action of a composition resulting from the admixture of material comprising substantially l0 parts anthracene, 2 parts sulfuric acid, 4 parts oil of mirbane, l part sodium hydroxide, and 200 parts naphthalene.

4. The process of treating petroleum products which comprises subjecting the same to the action of a composition resulting from the admixture of material comprising anthracene, sulfuric acid, sodium hydroxide, phosphate rock, naphthalene, sodium phosphate, ammonium carbonate and sugar.

5. The process of treating petroleum products which comprises subjecting the same to the action of a composition resulting from the admixture of materials comprising anthracene, sulfuric acid, sodium hydroxide,

phosphate rock, naphthalene, sodium phosphate, ammonium carbonate, sugar, arsenious acid, arsenic sulide and golden antimony sulfide. Y

6. The process of treatin petroleum products which comprises su jecting the same to the action of a composition resulting from the admixture of materials comprising anthracene, oil of mirbane, sodium hydroxide and naphthalene.

7. The process of treatin petroleum products which comprises sujecting the same to the action of a composition resulting from the admixture of materials com rising anthracene, oil of mirbane, sodium hydioxide and .a hydrocarbon of substantially the same pecifc gravity and fusing range as naphthaene.

In testimony whereof, I have hereunto signed my name. j

ALBERT H. ACKERMAN. 

